Surfactant-assisted synthesis of mesoporous silica/ceria–silica composites with high cerium content under basic conditions†
Ordered mesoporous silica/ceria–silica composites were synthesized using cerium(IV) hydroxide and tetraethyl orthosilicate (TEOS) as co-precursors in the presence of hexadecyltrimethylammonium bromide (CTAB) under basic conditions. These composites consisted of Ce-doped mesoporous silica particles (about 500 nm) with highly ordered 2D hexagonal (p6mm) and 3D bicontinuous cubic (Ia3d) structures and irregular ceria-rich silica–ceria particles. Wide angle XRD, diffuse reflectance UV-vis, and XPS analyses showed that 10–24% of cerium was at the Ce3+ oxidation level and the remaining predominant fraction of Ce was at the Ce4+ oxidation level. The cerium loading was varied in these composite materials up to 43 wt% (∼3.1 mmol g−1). The specific surface areas of the mesoporous silica/ceria–silica composite samples obtained on the basis of nitrogen adsorption isotherms were higher than 350 m2 g−1 and their pore widths were between 3.3 and 3.5 nm. The mesoporous silica/ceria–silica samples were reduced at 850 °C under flowing H2 in a N2 environment. The crystal structure of the reduced samples changed to a hexagonally structured phase with the oxidation state of Ce3+, while the ordered mesostructure of silica was preserved.